Triazole electroactive polymers

ABSTRACT

Tractable doped electroactive polymers, comprising recurring units of a N-substituted 1,3,4-triazole ring system, and a sufficient concentration of a charge-compensating ionic dopant associated therewith.

BACKGROUND OF THE INVENTION

This invention relates to electroactive organic polymeric materials.More specifically, this invention relates to associatingelectroactivating agents known in the art as dopants with an organicpolymer.

Recently, research has been conducted into organic polymeric materialsin order to modify their room temperature electrical conductivity byreacting them with electron donor or acceptor molecules. The electrondonor or acceptor molecules, generally known in the art as n- and p-typedopants respectively, can transform the organic polymeric materials sothat these modified organic polymeric materials exhibit semiconductingand metallic room temperature electrical conductivity. Polyacetylene isan example of an organic polymeric material whose room temperatureelectrical conductivity can be modified over several orders of magnitudeabove its insulator state, by the incorporation of dopant molecules, A.J. Heeger et al, U.S. Pat. No. 4,222,903, said patent incorporatedherein by reference. Other examples of organic polymeric materials whoseroom temperature electrical conductivity can be enhanced by severalorders of magnitude over their insulator state by means of incorporationof dopant molecules are poly-p-phenylene, polypyrrole, poly-1,6heptadiyne, and polyphenylene vinylene. However, all of the aboverecited examples are of organic polymeric materials which are completelyinsoluble or infusable and hence are completely intractable.

Other examples of organic polymers whose room temperature electricalconductivity can be modified with the aid of dopants are polyphenylenesulfide and poly-m-phenylene. However, the above recited materialsthough being tractable in their original virgin state, undergoirreversible chemistry when reacted with dopants which modify their roomtemperature electrical conductivity. This irreversible chemistry impartsupon these dopant modified organic polymeric materials a state ofintractability. Upon removal of the doping agents, these materials donot revert to the chemical structure which they originally exhibitedprior to being modified by the dopants. The inorganic materialpolysulfur nitride is also considered a polymeric conductor. As with thepreviously recited polymeric materials, polysulfur nitride is alsocompletely intractable.

The synthesis of poly(1,3,4-oxadiazole-2,5-diylvinylene) andpoly(1,3,4-oxadiazole-2,5-diyl-ethynylene) is described by I. Schopov etal. in Makromolecular Chemie, vol. 179, No. 1, pp. 63-71 (1978). Theseundoped oxadiazole polymers are shown by Schopov to exhibit anelectrical conductivity characteristic of insulators.

For use in a wide variety of electronic device applications, it ishighly desirable to have available organic polymeric electricallyconducting materials having a preselected room temperature conductivitywhich can be varied over a broad range. This range should preferablyextend from the insulator state of the unmodified organic polymericmaterial through the semiconducting regime and extending into the highlyconducting metallic state. It is also desirable that these organicpolymeric electrically conducting materials should be tractable andhence processable so that useful articles of any desired shape and sizecan be fabricated. Tractable organic polymers are those which can bereadily shaped, formed, molded, pressed, cast, etc., into desiredarticles from the liquid state, i.e. either from the melt, fluid glassystate, or from solution after the completion of the polymerizationreaction of the organic polymeric material.

SUMMARY OF THE INVENTION

We have invented an electroactive polymeric material comprising a dopantmodified organic polymer whose room temperature electrical conductivityis controlled in a highly selective and reversible manner. Electroactivepolymer is defined as a polymer having a conductivity which has beenmodified with electron acceptor or donor dopants to be greater than theconductivity of the virgin state of the polymer. The electroactiveorganic polymeric material is fabricated from a virgin polymer, which initself is completely tractable and processable and which exhibitsexcellent mechanical and thermal properties as well as being highlystable to oxidative degradation, by modifying the polymer with aconductivity modifier, i.e. electron donor dopants or electron acceptordopants. The electroactive organic polymeric material is comprised ofrecurring units of an N-substituted 1,3,4-triazole ring system and aconductivity modifier. More specifically, the electroactive polymer is acharged polymer backbone incorporating a sufficient concentration ofcharge-compensating ionic dopants, i.e., ions of opposite charge to thecharge of the polymer backbone. A sufficient concentration of ionicdopants is defined as that concentration which, when associated with thepolymer, effects a significant increase in the polymer conductivity,i.e., on the order of about 10% or greater. The recurring units arediradicals. The diradicals are directly linked to one another, or may beconnected to one another via connecting units. A "connecting unit" isdefined as any atom or group of atoms which can link the hereinabovediradicals together into a polymer chain.

Among other factors, the present invention is based on our discoverythat N-substituted 1,3,4-triazole polymers can be effectively doped withconductivity modifiers to provide electroactive polymers having anelectrical conductivity several orders of magnitude greater than theconductivity of the undoped virgin polymers. In addition, theelectroactive polymers of the invention are highly tractable andprocessable and therefore overcome the disadvantages of prior artmaterials.

An n-type electroactive organic polymer is obtained by reacting thevirgin polymer with reducing or electron donor dopants. Electron donordopants induce n-type conductivity in the polymer by donating anelectron to the polymer and reducing same to a polyanion and the dopantis oxidized to a cation. Similarly, a p-type electroactive organicpolymer is obtained by reacting the virgin polymer with oxidizingelectron acceptor dopants. Electron acceptor dopants induce p-typeconductivity in the polymer by oxidizing the polymer to a polycation andthe dopant is reduced to an anion. The desired value of the roomtemperature electrical conductivity of the dopant modified electroactiveorganic polymer is preselected by controlling the level of incorporationof the dopants into the virgin polymer. Alternatively, the desired valueof the room temperature electrical conductivity of the dopant modifiedelectroactive organic polymer is preselected by controlling the lengthof the reaction time between the virgin polymer and dopants.Furthermore, the highly selective and reversible modification of theroom temperature electrical conductivity of the virgin polymer canproceed by either chemical or electrochemical means. The highlyselective and reversible modification of the electrical conductivity ofthe dopant containing organic polymeric material together with thetractability and processability of the virgin polymer is highlydesirable in that the fabrication of useful articles and devices such asprimary and secondary batteries, photovoltaic devices, Schottky typedevices can be accomplished. Furthermore, the materials described inthis invention can be utilized as active components in such devices andarticles as electrochromic displays and photolithographic processes.

DETAILED DESCRIPTION OF THE INVENTION

Electroactive organic polymers are tractable and processable virginpolymers consisting of recurring units of an N-substituted1,3,4-triazole ring system modified by suitable conductivity modifiers.The polymers are composed of repeating diradical units derived fromN-substituted 1,3,4-triazole ring systems wherein the triazole issubstituted on the 1-nitrogen atom with lower alkyl of 1-6 carbon atomsor phenyl. A diradical is defined as a molecule that has two unsatisfiedpositions available for linking into the polymer chain. Optionally, thediradicals are separated in the polymer chain by connecting units.

Suitable examples of N-substituted 1,3,4-triazole recurring units are1-phenyl-1,3,4-triazole, 1-methyl-1,3,4-triazole,1-ethyl-1,3,4,-triazole, 1-propyl-1,3,4-triazole,1-butyl-1,3,4-triazole, 1-pentyl-1,3,4-triazole, 1-hexyl-1,3,4-triazole,and mixtures thereof. The recurring units can be interspersed with oneor more connecting units such as O, S, aryl, substituted aryl, alkenyl,thioalkenyl, thioaryl, and the like. Preferred connecting units are1,4-phenylene, 4,4'-biphenylene, --CH═CH--, and --C.tbd.C--. Aparticularly preferred connecting unit is 1,4-phenylene. The connectingunits can be the same or different between adjacent recurring units inthe polymer chain.

The polymer can be a homopolymer of the triazole diradicals or acopolymer of the diradicals. A homopolymer is defined as a polymercomprising the same recurring diradical. A copolymer is defined as apolymer comprising different diradicals. In addition, the polymer is acopolymer if the same or different recurring diradicals are interspersedwith connecting units.

The polymer is rendered electroactive by incorporating into the virginpolymer a conductivity modifier. More specifically, the polymer isrendered electroactive by adding electrons to (reducing) or removingelectrons from (oxidizing) the virgin polymer backbone. This can beaccomplished by incorporating into the virgin polymer a conductivitymodifier which is either an electron donor dopant or an electronacceptor dopant. An electron donor dopant donates an electron to thepolymer, the polymer becoming reduced to a polyanion and the dopantbecoming oxidized to a cation. An electron acceptor dopant removes anelectron from the polymer, the polymer becoming oxidized to a polycationand the dopant becoming reduced to an anion. Alternatively, the polymercan be rendered electroactive by electrochemical oxidation or reduction.In this case an electron is removed from or added to the polymer from anelectrode, and charge-compensating anions or cations, respectively, areincorporated into the polymer from the supporting electrolyte solution.

In both cases the resulting electroactive polymer consists of a chargedpolymer backbone incorporating charge-compensating ionic dopants. Asuitable positively charged compensating dopant can be a cation such asthe alkali metal ions, alkali earth metal ions, Group III metal ions,strong Lewis acids, and organic cations such as ##STR1## where R^(xi) isa straight- or branched-chain alkyl group of C₁ -C₆. Mixtures of thesecharge-compensating dopants can be employed. These ionic dopants producen-type conductivity when associated with a reduced or negatively chargedpolymer polyanion.

A suitable negatively charged compensating dopant, i.e. anionic dopants,can be an anion such as the halogen ions, other ions such as AsF₄ ⁻, andpreferably ions such as AsF₆ ⁻, ClO₄ ⁻, PF₆ ⁻, SO₃ CF₃ ⁻, BF₄ ⁻, NO₃ ⁻,POF₄ ⁻, CN⁻, SiF₅ ⁻, SbCl₆ ⁻, SbF₆ ⁻, HSO₄ ⁻, organic anions ions suchas CH₃ CO₂ ⁻, (acetate), C₆ H₅ CO₂ ⁻ (benzoate), CH₃ C₆ H₄ SO₃ ⁻(tosylate), strong Lewis bases, and the like. Mixtures of thecharge-compensating dopants can be employed. These ionic dopants producea p-type conductivity when associated with an oxidized or positivelycharged polymer polycation.

The dopant modified electroactive polymer has a charge opposite to theconductivity modifier, i.e. ionic dopant. The charges on the dopantmodified electroactive polymer and the ionic dopant balance so that thedopant modified electroactive polymer is an electrically neutral system.The association of the virgin polymer with electron donor dopantsproduces an electroactive polymer which exhibits n-type conductivity.More specifically, reduction of the virgin polymer and the incorporationof cationic charge-compensating dopants produces a polymer whichexhibits n-type conductivity. The association of the virgin polymer withelectron acceptor dopants produces an electroactive polymer with p-typeconductivity. More specifically, oxidation of the polymer andincorporation of anionic charge-compensating dopants produces a polymerwith p-type conductivity.

The preferred electroactive polymers of the invention have the followingformula: ##STR2## where a is either 0 or 1; b is either 0 or 1; c iseither 0 or 1; n is an integer from 2 to 1,000; d is an integer from 1to 2,000; s is an integer from 1 to 3; R and R' are each independentlyN-substituted 1,3,4-triazoles; X' and Y' are each independentlyconnecting units comprising a single atom, or a group of atoms; and M isan atom or a group of atoms acting as a charge-compensating ionic dopantwhose electrical charge is opposite to the charge exhibited by therecurring repeat units of the polymer backbone: ##STR3##

The repeat units from the polyanion or polycation of the electroactivepolymer.

The R and R' groups are independently N-substituted 1,3,4-triazolerings, wherein the substituent on the 1-nitrogen atom is selected fromthe group consisting of lower alkyl of 1-6 carbon atoms and phenyl. Moreparticularly, R and R' are N-substituted 1,3,4-triazole diradicals ofthe following formula: ##STR4## wherein R₁ is lower alkyl of 1-6 carbonatoms or phenyl.

More specifically, R and R' are the triazole diradicals previouslyrecited or mixtures of the diradicals which are linked to one anothereither directly or via the connecting units X' and Y' by formingbridges.

The connecting units X' and Y' can be selected from the groupcomprising: ##STR5## wherein R₁ is lower alkyl C₁ -C₆, aryl, cycloalkyland alkoxy; R^(v), R^(vi) and R^(vii) are H or methyl, methoxy, halogenand mixtures thereof; and R^(x) is C₁ -C₄ alkyl. 4,4'-Biphenylene,vinylene; 1,4-phenylene, and acetylene connecting groups are preferredconnecting units. Especially preferred connecting units are1,4-phenylene and 4,4'-N-alkylaminodiphenylene.

The molecular weight determines the physical properties of theelectroactive polymer. The magnitude of n is a function of the molecularweight. Preferably, n is from 5 to 500. More preferably, n is from 10 to300. Molecular weights of the polymer should be between about 250 and250,000. A preferred molecular weight is above about 10,000. Tractablefilms are formed with electroactive polymers wherein n is adjusted sothat the molecular weight exceeds 10,000.

The enhancement in conductivity of the electroactive polymer above theconductivity of polymer in the virgin state is determined by d. Thevalue for d is not greater than 2 n. The conductivity is increased andadjusted by increasing d. Conductivities in the semiconductor region cangenerally be achieved with d values of about 5 percent the n value,e.g., d equals 5 when n equals 100.

Preferred electroactive polymers are doped polymers that haveconductivities greater than about 1×10⁻¹⁰ ohm⁻¹ cm⁻¹, most preferablygreater than 1×10⁻⁴ ohm⁻¹ cm⁻¹. Greater concentrations of thecharge-compensating ionic dopant M increase the conductivity to themetallic conductivity regime. The charge-compensating cationic oranionic dopant M is selected from the previously recited dopants and thelike. M remains the same for all the following preferred polymers.

The R and R' groups may be the same or different. When a is 1, b and care zero, R' and Y' drop out and the polymer has the following formula:##STR6## A preferred polymer of this formula is poly1,4-phenylene-2,5-(1-phenyl-1,3,4-triazole) doped with a conductivitymodifier.

When a and c are 1 and b is zero, Y' drops out and the polymer has theformula: ##STR7## A preferred polymer of this formula ispoly-5,5'-(1,4-phenylene-bis-2,2'-(1-phenyl-1,3,4-triazole)) doped witha conductivity modifier.

When a is zero and b and c are 1, X' drops out and the polymer has theformula: ##STR8##

When a, b, and c are zero, R', X', Y' drop out and the polymer has theformula: ##STR9## A preferred polymer of this formula ispoly-2,5-(1-phenyl-1,3,4-triazole) doped with a conductivity modifier.

Although the polymers of the invention can be made up solely of1,3,4-triazoles, the preferred materials are copolymers wherein thetriazole rings are connected through another group, designated aconnecting unit. In general, the connecting units should preserve theconjugation of the heterodiazole rings. The connecting units themselvesmust either be conjugated or maintain pi orbital overlap with theheterocyclic ring systems.

Connecting units may be selected from heteroatoms, such as the Group VBand VIB elements of the Periodic Table, including oxygen, sulfur,selenium, tellurium, monosubstituted nitrogen, phosphorus, arsenic orantimony. Preferably, the connecting uints are conjugated carbonsystems, such as olefins or aryl ring systems.

Olefinic connecting units are those obtained by removing a hydrogen atomfrom each end of the olefinic double bond or from each end of aconjugated double bond system. Typical olefinic connecting units includethose obtained from ethylene, butadiene, cyclopentadiene, divinylether,and the like.

Aryl ring connecting units are obtained from the corresponding aromaticcompounds by removing two hydrogen atoms from carbon atoms in thearomatic ring system. Typical aromatic connecting units include thoseobtained from benzene, naphthalene, diphenyl, diphenyl ether, diphenylsulfide, diphenylalkylamine, anthracene, and the like. Other arylconnecting units are obtained from alkyl or aklenyl aromatics, byremoving two hydrogen atoms, either from the ring, from the alkenylgroup, or one hydrogen each from the ring and from the alkenyl group.Typical connecting units of this type include those obtained fromstyrene, divinylbenzene, stilbene, and the like.

POLYMER FABRICATION

The starting material for preparing the electroactive polymers of thisinvention are polymers and copolymers comprising recurring units ofN-substituted 1,3,4-triazoles, wherein the substituent on the 1-nitrogenatom is lower alkyl of 1-6 carbon atoms or phenyl. These polymers andcopolymers are well known materials having been synthesized in a varietyof ways.

The triazole-containing polymers useful for making electroactivepolymers by appropriate doping techniques are prepared by two alternateroutes.

In one process, the corresponding oxadiazole-containing polymer isreacted with an appropriate primary amine. The reaction is carried outin an acid solvent such as polyphosphoric acid, sulfuric acid and thelike, at temperatures in the range of 200° C. to 350° C., preferably250° C. to 300° C. The reaction is carried out in a closed vessel atautogenous pressure. The polymer product is isolated by filtrationfollowed by washing to remove the acidic medium. For this process, theoxadiazole polymer feedstock is made by the reaction of a dibasic acidwith hydrazine. This reaction is carried out in one of the above namedsolvents at temperatures in the range of 100° C. to 250° C., preferably140° C. to 180° C. (Ref. J. Polymer Sci., 3, 45 (1965)). Dibasic acidsare readily obtainable; hydrazine is a commercial material. For thisreaction, hydrazine salts such as the sulfate, halide, phosphate, etc.are preferred.

The alternate method for preparing the triazole polymers of thisinvention is by the reaction of an appropriate primary amine with apolyhydrazide. The reaction is carried out in a high boiling acidicsolvent at temperatures in the range of 100° C. to 300° C., preferably150° C. to 200° C. The polyhydrazide feedstock is made by the reacitonof essentially equal moles of an appropriate dibasic acid chloride withone mole of hydrazine. This reaction is carried out in an organictertiary amine solvent which also functions as a hydrogen chloridescavenger. Amines useful in this reaction include pyridine,diethylamine, triethyl amine, and the like.

TRACTABLE POLYMER FABRICATION

Subsequent to polymerization, articles such as fibers, ribbons, orfree-standing films are cast from solution. The solution is formed bydissolving the desired polymer in a solvent which consists of sulfuricacid, formic acid, methane sulfonic or polyphosphoric acid. The solutiontemperature is generally from about 20° C. to about 100° C. The polymersare coagulated into solid shapes such as fibers, ribbons, orfree-standing films in a basic coagulation bath. For free-standingfilms, the polymers are fabricated from solutions containing about 2 to25% polymer dissolved in the solvent. At concentrations which exceed10%, the cast films take on an anisotropic morphology. The anisotropicproperty enhances the conductivity in the anisotropic direction. Anamine, for example triethylamine, dissolved in a protonic solvent suchas H₂ O and preferably ethyl alcohol comprises the coagulation bath. Thebath is maintained at a lower temperature than the dissolutiontemperature of the polymer in the solvent. Usually room temperature isselected as the operating temperature of the coagulation bath. Thefabricated articles are dried. Elevated temperatures, usually 60° C.,and reduced pressure accelerated the drying process. Drying is continueduntil no further weight loss is observed.

Alternatively, films are cast into water, comprising the coagulationbath, followed by neutralization in aqueous bicarbonate. Neutralizedfilms are washed in water and dried at elevated temperatures, 60°-100°C., under reduced pressure.

POLYMER CONDUCTIVITY MODIFICATION

After fabrication of the desired articles from the heterocyclic polymersby means of the procedure described above, the articles are renderedelectroactive by, for example, chemical or electrochemical procedures.The articles can be rendered electroactive in an atmosphere which isinert with respect to the polymer and dopant, by contacting them withsuitable conductivity modifiers, i.e. dopants. An inert atmosphere isdefined as an atmosphere which does not react with the polymer, thedopant, or the electroactive polymer. For example, the atmosphere can beargon, helium, and nitrogen and the like. The doping can also be carriedout in an inert liquid medium such as tetrahydrofuran, acetonitrile andthe like. The inert liquid medium should be able to wet and swell thepolymer but not react with it. The dopants can be oxidizing or electronaccepting molecules, or reducing or electron donating molecules. Bothtypes of dopants may be in the form of gases or vapors, pure liquids orliquid solutions. Preferably, oxygen and water moisture are excludedduring and after the doping process because the conductive polymers tendto degrade, i.e. lose conductivity, when exposed thereto.

For example, the polymer can be contacted with conductivity modifierssuch as alkali naphthalides, or alkali anthracenides such as sodiumnaphthalide, potassium naphthalide, or sodium anthracenide, in atetrahydrofuran solution. The conductivity modifier concentration can befrom about 0.001 to about 1 molar and preferably from about 0.01 toabout 0.5 molar in the THF or other suitable solvent. Alternative dopingmethods are taught in U.S. Pat. No. 4,204,216 and incorporated herein byreference.

The incorporation of the dopants into the polymer can be observed by acolor change in the polymer as well as an enhanced conductivity. Forexample, a virgin polymer film having a yellow, orange or brown color,changes to a green, blue or black color with a metallic luster upondoping and the measured conductivity increases by many orders ofmagnitude.

Alternatively, the polymers can be oxidized or reduced to theirconductive forms using electrochemical techniques. In this method,herein referred to as electrochemical doping, the polymer is immersed ina suitable electrolyte solution and used as one electrode of anelectrochemical cell. Upon passing an electric current through such acell the polymer becomes reduced (or oxidized, depending upon thedirection of current flow) and charge-compensating cations (or anions)from the supporting electrolyte become incorporated into the polymer.This doping also proceeds with the characteristic color change describedabove. Thus, the polymer can be electrochemically doped with whateverappropriately charged ion is present in the electrolyte solution.Electrolyte solutions are comprised of a salt dissolved in a solvent.Suitable solvents are acetonitrile, tetrahydrofuran,2-methyl-tetrahydrofuran, propylene carbonate, dimethylformamide,dimethylsulfoxide and the like. Alternative electrolytes are specifiedin U.S. application Ser. No. 334,509, filed Dec. 28, 1981, entitled"Batteries Fabricated With Electroactive Polymers", and completelyincorporated herein by reference. Suitable cations are Li⁺, Na⁺, K⁺,(CH₃)₄ N⁺, (C₂ H₅)₄ N⁺ and (C₄ H₉)₄ N⁺. Suitable anions are Cl.sup. -,Br⁻, ClO₄ ⁻, BF₄ ⁻, and PF₆ ⁻. The extent of doping can be easilycontrolled by adjusting the amount of charge electrochemically injectedinto the polymer, either by controlling the magnitude of the currentused (galvanostatic charging) or by controlling the potential of thepolymer electrode with respect to a reference electrode (potentiostaticcharging).

The above-described electrochemical doping process is completelyreversible. The polymer can be "undoped" and returned to its original,neutral, non-conducting state simply by applying a current opposite insign to that used for the doping process. Upon complete undoping thecolor of the polymer reverts back to its original color. Thus, forexample, a reduced, conducting poly-N-substituted triazole polymer canbe reoxidized completely to its neutral, non-conducting form, and thecharge-compensating cations incorporated during the electrochemicalreduction process are expelled from the article during electrochemicalre-oxidation.

Having described the methods of fabrication and the basic heterocyclicsystems, the following examples are intended to be illustrative of theinvention and not meant to limit the scope thereof. Modification whichwould be obvious to one of ordinary skill in the art are contemplated tobe within the scope of the invention.

EXAMPLES Example 1 Poly-1,4-phenylene-2,5-(1-phenyl-1,3,4-triazole)

A 300 ml 3-neck flask, equipped with a stirrer, thermometer, condenserand an addition funnel, was charged with 150 g of polyphosphoric acid.After heating to 140° C., 6.6 g (0.25 mol) of hydrazine sulfate wasadded, followed by 6.93 g (0.0417 mol) of terephthalic acid. Stirringand heating was continued at 140° C. for 5 hours and then at 175° C. for2 hours. After standing at room temperature for 16 hours, 50 g ofpolyphosphoric acid was added. Next the reaction mixture was heated at140° C. and 27.9 g (0.3 mol) of aniline was added. Heating was continuedfor 2 hours and finally at 195° C. for about 6 hours.

At the end of this time, the crude reaction mixture was poured intowater. The resulting slurry was filtered. The precipitate was washedwith water, neutralized with triethylamine, and extracted (Soxhlet) withethanol for 4 days. After drying, 14.5 grams of poly1,4-phenylene-2,5-(1-phenyl-1,3,4-triazole) was obtained.

EXAMPLE 2 Poly-1,4-phenylene-2,5-(1-phenyl-1,3,4-triazole) Preparationof Poly-terephthaloylhydrazide

A 200 ml 3-neck flask, equipped with a stirrer, thermometer andcondenser with a calcium chloride drying tube, was charged with 100 mlof hexamethylphosphoramide, 1.5 g of powdered lithium chloride, and 3.88g (0.02 mol) of terephthaloyl hydrazide, and the mixture was stirred at50° C. until a complete solution was obtained. The solution was cooledto 0° to 5° C., and 4.06 g (0.02 mol) of terephthaloyl chloride wasadded in 4 essentially equal portions at this temperature over 30minutes, and then stirred for one additional hour. The temperature wasraised to room temperature, and stirring was continued for two morehours. The reaction mixture was poured into ice water with stirring, andfiltered. The filter cake was washed with water until the filtratebecame neutral to pH paper, and dried in air. After drying, 6.71 g ofpoly-terephthaloylhydrazide was obtained.

Preparation of poly-1,4-phenylene-2,5-(1-phenyl-1,3,4-triazole

A 300 ml 3-neck flask, equipped with a stirrer, thermometer, condenserand an addition funnel, was charged with 110 g of polyphosphoric acid.After heating to 150° C., 27.5 g (0.296 mol) of aniline was added whilethe temperature was held below 190° C. The temperature was adjusted to175° C., and 3.6 g of poly-terephthaloylhydrazide was added. Stirringand heating were continued at 175° C. for 21 hours, then at 200° C. for8 hours, and then at 220° C. for 92 hours. At the end of this time, thecrude reaction mixture was poured into water, and the resulting slurrywas filtered. The precipitate was washed with water, neutralized withaqueous triethylamine, and extracted (Soxhlet) with ethanol overnight.After drying, 4.2 g of tan-colored crude polymer was obtained, which waspurified by dissolving in concentrated sulfuric acid (2 weight percentsolution), filtering, and reprecipitating the polymer by pouring intoethanol. After drying, 0.78 g of poly1,4-phenylene-2,5-(1-phenyl-1,3,4-triazole) was obtained.

Electrochemical Doping of Polymer on a Wire

The product of the example was dissolved in concentrated sulfuric acidto give about a 2 weight percent solution. A platinum wire, 0.5 mm indiameter, was dipped into this solution. After removing it from thesolution, excess liquid was gently wiped off and then the wire wasplaced in a water bath for 30 minutes at ambient temperature. Next itwas soaked in a 5% sodium bicarbonate solution for 16 hours. At the endof this time the wire was rinsed with water, rinsed with acetone, andthen dried under vacuum.

The resulting polymer-coated wire was submitted to a cyclic voltammetricanalysis. For this analysis, the electrolyte was an 0.1 molar solutionof tetraethylammonium tetrafluoroborate in acetonitrile. Measurementswere made with reference to a silver/silver nitrate reference electrodeand subsequently converted into voltages with the standard calomelelectrode (SCE). A reversible reduction potential of -2.2 V vs. SCE wasobtained.

What is claimed is:
 1. A tractable electroactive polymer which comprisesa charged polymer backbone of recurring units of a monocyclicN-substituted 1,3,4-triazole, wherein the 1-nitrogen atom is substitutedwith lower alkyl of 1-6 carbon atoms or phenyl, and a sufficientconcentration of a charge-compensating ionic dopant associatedtherewith, wherein the polymer backbone is capable of undergoingreversible oxidation or reversible reduction or both to form the chargedpolymer backbone.
 2. The electroactive polymer according to claim 1,wherein the recurring unit is 1-phenyl-1,3,4-triazole.
 3. Theelectroactive polymer according to claim 1 wherein the recurring unit is1-methyl-1,3,4-triazole.
 4. The electroactive polymer according to claim1, wherein the recurring units are interspersed with connecting unitsselected from the group consisting of: ##STR10## wherein R₁ is loweralkyl C₁ -C₆, aryl, cycloalkyl, and alkoxy; R^(v), R^(vi) and R^(vii)are H, methyl, methoxy, halogen, and mixtures thereof; and R^(x) is C₁-C₄ alkyl.
 5. The electroactive polymer according to claim 4, whereinthe connecting units are selected from the group consisting of1,4-phenylene, 4,4'-biphenylene, vinylene, and ethynylene.
 6. Theelectroactive polymer according to claim 5, wherein the connecting unitis 1,4-phenylene.
 7. The electroactive polymer according to claim 4,wherein the connecting unit is 4,4'-N-alkylaminodiphenylene.
 8. Theelectroactive polymer according to claim 1, wherein thecharge-compensating ionic dopant is a cation selected from the groupconsisting of the alkali metal ions, alkali earth metal ions, Group IIImetal ions, ##STR11## wherein R^(xi) is a straight- or branched-chainalkyl group of C₁ -C₆ groups, or mixtures of said cations.
 9. Theelectroactive polymer according to claim 1, wherein the polymer backbonehas a molecular weight of from about 250 to about 250,000.
 10. Theelectroactive polymer according to claim 9, wherein the polymer backbonehas a molecular weight above about 10,000.
 11. A tractable electroactivepolymer which comprises a charged polymer backbone andcharge-compensating ionic dopants associated therewith of the formula:##STR12## wherein a is 0 or 1; b is 0 or 1; c is 0 or 1; n is an integerfrom 2 to 1,000; d is an integer from 1 to 2,000; S is an integer from 1to 3; R and R' are each independently monocyclic N-substituted1,3,4-triazoles, wherein the 1-nitrogen atom is substituted with loweralkyl of 1-6 carbon atoms or phenyl; X' and Y' are each independentlyconnecting units selected from the group consisting of: ##STR13##wherein R₁ is lower alkyl C₁ -C₆, alkyl cycloalkyl, and alkoxy; R^(v),R^(vi) and R^(vii) are H, methyl, methoxy, halogen, and mixturesthereof; and R^(x) is C₁ -C₄ alkyl; and M is a charge-compensating ionicdopant of opposite electrical charge to the charge of the polymerbackbone; wherein the polymer backbone is capable of undergoingreversible oxidation or reversible reduction or both to form the chargedpolymer backbone.
 12. The electroactive polymer according to claim 11,wherein R and R' are each diradicals of the formula: ##STR14## whereinR₁ is lower alkyl of 1-6 carbon atoms or phenyl.
 13. The electroactivepolymer according to claim 11, wherein X' and Y' are independentlyselected from the group consisting of 1,4-phenylene, 4,4'-biphenylene,vinylene, and ethynylene.
 14. The electroactive polymer according toclaim 13, wherein X' and Y' are 1,4-phenylene.
 15. The electroactivepolymer according to claim 11, wherein X' and Y' are4,4'-N-alkylaminodiphenylene.
 16. The electroactive polymer according toclaim 11, wherein n is from about 5 to about
 500. 17. The electroactivepolymer according to claim 11, wherein a is 1, b and c are zero, and thepolymer has the formula: ##STR15##
 18. The electroactive polymeraccording to claim 11, wherein a, b and c are zero, and the polymer hasthe formula: ##STR16##
 19. The electroactive polymer according to claim11, wherein the charge-compensating ionic dopant M is a cation selectedfrom the group consisting of the alkali metal ions, alkali earth metalions, Group III metal ions, and ##STR17## wherein R^(xi) is a straight-or branched-chain alkyl of C₁ -C₆, or mixtures of said cations.